DE1544523C3 - Azo reactive dyes and their use for dyeing and printing cellulosic materials - Google Patents

Description

The present invention relates to water-soluble new reactive dyes of the general composition

RSO

N = N - A-S

(D

where A is the residue of an aminobenzenes, aminonaphthalenes, pyrazolones, hydroxybenzenes, hydroxynaphthalene, aminopyrazoles and acetoacetamides, the substituents S being sulfonic acid, carboxylic acid, sulfamide, sulfone, alkylamino, nitro, cyano, halogen, hydroxy, Alkoxy, mono-, di- or trihalopyrimidinamino, monohalogen or dihalotriazinylamino groups, R _{1 is} hydrogen or the sulfo group, R is an alkyl radical having 1 to 5 carbon atoms, optionally phenyl substituted by chlorine or methyl, benzyl or the 2-benzothiazolyl radical and η denotes the number 1 or 2, in particular those of the formula

OH (SO ₃ H) ₁ ,

RSO

where B is hydrogen or an acetyl or benzoylamino, alkoxy substituent, u is an integer from 1 to 3, R is an alkyl radical with 1 to 5 carbon atoms, optionally phenyl substituted by chlorine or methyl, benzyl or the 2-benzothiazolyl radical and R ₁ Means hydrogen or the sulfo group, as well as the formula

CH, or - COOH

(III)

wherein C is hydrogen or chlorine, bromine or methyl, t is the number 1 or 2, R is an alkyl having 1 to 5 carbon atoms, phenyl, benzyl or the 2-benzothiazolyl radical optionally substituted by chlorine or methyl and R _{1 is} hydrogen or the sulfo group, X is Radical O = or HN = and η is 1 or 2, as well as the formula

RSO ₂

NH ₂

N = N

(IV)

(SO ₃ H) ₁

OH

N = N-E

May be substituted nitro group or sulfo groups or the remainder of the formula

40

where D is hydrogen, the hydroxyl or acetylamino or the benzoylamino group, t is the number 1 or 2, R is an alkyl having 1 to 5 carbon atoms, optionally phenyl, benzyl or 2-benzothiazolyl substituted by chlorine or methyl and R _{1 is} hydrogen or sulfo means, as well as the formula

(SO ₃ H), (V)

where E is the remainder of a benzene or naphthalene nucleus, which is optionally replaced by chlorine, the hydroxy or ■ yes-

R-SO ₂ - <

ί the number 1 or 2, R is an alkyl with 1 to 5 carbon atoms, phenyl, benzyl or the 2-benzothiazolyl radical which is optionally substituted by chlorine or methyl and R _{1 is} hydrogen or the sulfo group, as well as the formula

RSO

OH

N = N

55

6o

(VI)

wherein F is a phenyl radical substituted by one or more sulfonic acid groups, in which the azo and —O groups are in o-position to one another, R is an alkyl having 1 to 5 carbon atoms, optionally phenyl substituted by chlorine or methyl, benzyl or the 2 -Benzthiazolylrest and R _{1 is} hydrogen or the sulfo group

interprets, as well as the formula

(VII)

where G is the acetyl or benzoyl group, K ₁ and K _{2 are} hydrogen or methyl, methoxy, acetyl or benzoylamino groups or an ω-methanesulfonic acid group, R is an alkyl having 1 to 5 carbon atoms, optionally phenyl, benzyl or substituted by chlorine or methyl the 2-benzothiazolyl radical and R _{1 is} hydrogen or the sulfo group, as well as the formula

RSO ₂

(VIII)

where B is hydrogen, the acetyl or benzoylamino or alkoxy group, K _{1 is} hydrogen or a methyl, methoxy, acetyl or benzoylamino group or an ω-methanesulfonic acid group, u is an integer from 1 to 3, R is an alkyl radical having 1 to 5 carbon atoms , phenyl optionally substituted by chlorine or methyl, benzyl or the 2-benzthiazolyl radical and R ₁ denotes hydrogen or the sulfo group, and of the formula

NH,

N = NE
(IX)

(SO ₃ H),

optionally substituted by chlorine or methyl phenyl, benzyl or the 2-benzothiazolyl radical and R _{1 is} hydrogen or the sulfo group, as well as the formula

30th

35

40

(SO ₃ H),

wherein ί the number 1 or 2, R is an alkyl radical with 1 to wherein E is the radical of one of the following 5 carbon atoms, optionally with chlorine or marked diazo component, preferably such a methyl substituted phenyl, benzyl or the 2-benzene benzene or naphthalene series, t denotes the number 1 or 2, thiazolyl radical and R ₁ denotes hydrogen or the sulfo group R denotes an alkyl radical having 1 to 5 carbon atoms, as well as the formula

O-Cu-O

RSO-

PCI)

N = N

(SO ₃ H) ₁ ,

where B is hydrogen, the acetylamino, benzoylamino, alkoxy or arylamino group, u is an integer from 1 to 3, R is an alkyl radical with 1 to 5 carbon atoms, optionally phenyl substituted by chlorine or methyl, benzyl or the 2-benzthiazolyl radical and R ₁ denotes hydrogen or the sulfo group.
As suitable for the construction of the new dyes

Diazo components of the benzothiazole series of the formula

^{RS <V} - _s ^ y

those in the 2-position have a reactive sulfonyl substituent include, for example:

609 623/20

T-Amino-I-methylsulfonylbenzthiazole, o-Amino ^ -methylsulfonylbenzthiazole, S-amino-1-methylsulfonylbenzthiazole.

4-Amino-2-methylsulfonylbenzthiazole, S-Amino-o-methyl ^ -methylsulfonylbenzthiazole, S-Amino ^ -methyl ^ -methylsulfonylbenzthiazoL S-Amino-o-chloro ^ -methylsulfonylbenzthiazole, S-amino-o-methoxy-l-methylsulfonylbenzthiazole,

o-Amino ^ -sulfo ^ -methylsulfonylbenzthiazole, 6-Amino-5-sulfo-2-methylsulfonylbenzthiazole. 6-amino-5-chloro-2-methylsulfonylbenzthiazole, o-Amino-S-methoxy ^ -methylsulfonylbenzthiazole,

6-amino-5-methyl-2-methylsulfonylbenzthiazole, 4-amino-6-methyl-2-methylsulfonylbenzthiazole, 4-amino-6-methoxy-2-methylsulfonyl-

benzthiazole,
4-Amino-6-chloro-2-methylsulfonylbenzthiazole.

Within the dyes of the formulas I to XI, those are of particular interest in which the Azo group in the 5- or 6-position of the benzene ring of the benzothiazole component.

The new dyes of the formula I are obtained by using diazotized aminobenzothiazoles of the formula

RSO,

NH,

35

and depending on the type of coupling components used with these in mineral acid, acetic acid, neutral, soda-alkaline and soda-alkaline medium. As an azo component preferably those from the series of aminobenzenes, hydroxybenzenes, hydroxynaphthalenes, Aminonaphthalenes, pyrazolones, aminopyrazoles and acetoacetic acid amides in question. From the big one The following are excerpts from the number of azo components to be mentioned here:

1-amino-3-methyl-benzene,

l-amino-3-methyl-6-methoxybenzene, 1-amino-benzene-3-sulfoacetylamino-benzene, Resorcinol,

l-amino-benzene-3-w-methanesulfonic acid, 1 - hydroxynaphthalene-4-sulfonic acid, l-hydroxynaphthalene-4,8-disulfonic acid, 1 - hydroxynaphthalene-3,6-disulfonic acid, 1 - hydroxynaphthalene ^ J-disulfonic acid, l-hydroxynaphthalene-3,8-disulfonic acid, l-hydroxynaphthalene-3,6,8-trisulfonic acid, 2-hydroxynaphthalene-3,6-disulfonic acid, 2-hydroxynaphthalene-6,8-disulfonic acid, 2-hydroxynaphthalene-5,7-disulfonic acid, 2-hydroxynaphthalene-6-sulfonic acid, 2-hydroxynaphthalene-5-sulfonic acid, l-amino-naphthalene-6,7- and -8-sulfonic acid, 2-amino-naphthalene-5-sulfonic acid, 2-amino-naphthalene-5,7-disulfonic acid, 1,3-dihydroxynaphthalin-5,7-disulfonic acid, l-hydroxy-8-acetamino-naphthalene-

3,6-disulfonic acid,
l-hydroxy-8-acetamino-naphthalene-

3,5-disulfonic acid,
l-hydroxy-8-benzoylamino-naphthalene-3,5-disulfonic acid,

l-hydroxy-8-benzoylamino-naphthalene-

3,6-disulfonic acid,
l-hydroxy-8-amino-naphthalene-

3,6-disulfonic acid,
l-hydroxy-8-amino-naphthalene-

3,5-disulfonic acid,
1 -hydroxy-7-amino-naphthalene-

3,6-disulfonic acid,

l-hydroxy-7-amino-naphthalene-3-sulfonic acid,
l-hydroxy-o-amino-naphthalene-S-sulfonic acid,
1 -hydroxy-6-amino-naphthalene-

3,5-disulfonic acid,
l-hydroxy-7- (3'-sulfophenyl-) amino-

naphthalene-3-sulfonic acid,
l-hydroxy-6- (4'-sulfophenyl -) - amino-

naphthalene-3-sulfonic acid,
l-hydroxy-6-acetamino-naphthalene-

3-sulfonic acid,
l-hydroxy-8-amino-naphthalene-

5,7-disulfonic acid,
l-hydroxy-8-acetamino-naphthalene-

5-sulfonic acid

1- (4'-sulfophenyl-) pyrazolone-5-carboxylic acid-3,
l- (4'-sulfo-2'-methylphenyl) pyrazolone

5-carboxylic acid-3,
l- (2 ', 5'-dichloro-4'-sulfophenyl -) - 3-methyl-

pyrazolone-5,

1- (4'-sulfophenyl-) 3-methyl-pyrazolone-5,
1- (4'-sulfo-2'-methyl-) 3-methyl-pyrazolon-5,
1- (2 ', 5'-disulfophenyl-) 3-methyl-pyrazolon-5,
1- (4'-sulfophenyl) 3-methy1-5-aminopyrazole.

If the monoazo dyes obtainable according to the process also contain diazotizable amino groups, see above these can be diazotized by a customary process and again with a suitable coupling component be implemented, whereby one arrives at disazo dyes.

Another way of building up disazo dyes is to use monoazo dyes represents that still contain couplable sites and then these with suitable diazo components combined, whereby the aminobenzothiazole diazo components to be used according to the invention, the have a reactive sulfonyl substituent in the 2-position, either for the first or the second or a later coupling step begins.

The azo components which are used to build up the monoazo dyes are primarily those from the series of dihydroxybenzenes, dihydroxynaphthalenes and amino-hydroxynaphthalenes already mentioned used.

The following can be used as second or further diazo components for the synthesis of disazo dyes:

Aminobenzene,

1-amino-benzene-2,3- and -4-sulfonic acid,

l-amino-benzene-2,4-disulfonic acid,

l-amino-benzene-2,5-disulfonic acid,

1-amino ^ -hydroxy-benzoW.S-disulfonic acid,

l-amino-2-hydroxy-benzene-5-sulfonic acid,

l-Amino ^ -hydroxy-S-chloro-benzene-S-sulfone-

acid,
1 -Amino ^ -hydroxy-S-nitro-benzene-S-sulfone-

acid,

2-amino-naphthalene-1,5-disulfonic acid,
2-amine-naphthalene-1-sulfonic acid

and those from the series of 4,5,6- and 7-amino

CH, SO, -C.

N = N

HO

-CH,

SO ₃ H

OH

2-methylsulfonylbenzothiazoles. Diazo components from this group can also be used twice.

If the dyes prepared according to the process contain groups which form metal complexes, so can these are converted into their copper complex compounds by the action of copper-releasing agents.

The introduction of the metal complex-forming groups can, for. B. be done so that one diazo components combined with azo components and choosing the components in such a way that the azo group is flanked by two metal complex-forming groups in the o-position, such as hydroxyl groups. If this is not the case, one can use the known method of oxidative copper plating get the desired copper complex dyes, introduce a second hydroxyl group and thus also Build metal complexes. Copper complexes from monoazo dyes can also be obtained if the diazo component is 4,5,6- or 7-amino-2-methyl-sulfonylbenzthiazole used.

The new dyes are extremely valuable products that are suitable for a wide variety of applications. As water-soluble dyes, especially those containing sulfonic acid groups, they are of particular interest for dyeing textile materials containing hydroxyl groups and nitrogen, in particular textile materials made from native and regenerated cellulose, as well as from wool, silk, synthetic polyamide and polyurethane fibers. Thanks to the reactive sulfonyl substituent or substituents in the 2-position of the thiazole ring, these products are particularly suitable as reactive dyes for dyeing cellulose materials using the techniques known for this purpose. The fastness properties obtained, especially wet fastness properties, are excellent. The productivity of the new reactive dyes should also be emphasized.

The dye of the formula

French patent specification 12 90 839 has the advantage of providing deeper dyeing on cotton by the cold padding process.
The dye of the formula according to the invention

CH ₁ SO

CH ₃

N = N

HO

(SO ₃ H) ₃ - (NiPc) -SO ₂ -HN

shows, compared to the next comparable dye known from Belgian patent specification 6 30 929, Example 21, the surprising advantage of providing deeper dyeings when dyeing cotton by the pad thermosetting process.
The dye of the formula according to the invention

shows the advantage over the dye of Example 1 of French Patent 12 90 839, to deliver deeper dyeing on cotton using the block thermosetting process; the dye the formula

C-SO ₂ CH ₃

SO ₃ H
shows, compared to the dye of Example 5, the French NHCOCH,

C ₂ H ₅ SO;

SO ₃ H

OH

N = N

HO ₃ S

SO ₃ H

shows, compared to the next comparable dye known from French patent specification 85 590, Example 6, the surprising advantage of providing deeper dyeings when dyeing cotton by the Klotz thermosetting process.
The dye of the formula

40 NHC

OH

CH ₃ SO ₂ - ^

45

N = N

HO ₃ S

SO ₃ H

SO ₃ H

and the dye of the formula

OH

HO ₃ S

SO ₃ H

NHCCH ₃

Il ο

show, compared with the dye known from German Auslegeschrift 1188 230, Example 21 or Example 21 in conjunction with Table Example 7, the surprising advantage of better etchability of the dyeings on cotton.

In the following examples, parts stand for parts by weight , unless otherwise stated; the temperature data are degrees Celsius.

example 1

13.2 parts of 2-methylsulfonyl-6-amino-benzothiazole are concentrated in 100 parts by volume of ice-water and 16 parts by volume. Hydrochloric acid stirred; a solution of 4.1 parts of sodium nitrite in 10 parts by volume of water is poured into it. The diazo compound goes into solution with a yellow color. After excess nitrous acid has been removed, the diazo solution is added to a solution of 17.6 parts of 2-hydroxynaphthalene-3,6-disulfonic acid and 10 parts of soda in 200 parts of ice-water. The coupling ends quickly. The dye is suction filtered and dried at 50 ⁰ C. A red powder is obtained. The resulting dye corresponds to the following in the form of the free sulfonic acid

^{the formula:} OH SO ₃ H

15th

CH ₃ SO

N = N

SO ₃ H

It dyes cellulose in red shades with very good fastness properties, especially very good ones Wet fastness properties.

If you proceed in the same way as in this example, but using the one in the following The components listed in the table also give reactive dyes which, according to one of the customary application methods result in real colorations, the color shades of which are also recorded in the table are.

35

40

No. Diazo component Clutch hue component 2 2-methylsulfo- 2-hydroxynaph- yellow nyl-6-amino- thalin-6,8-di- benzthiazole sulfonic acid 3. 2-methylsulfo- 1-hydroxy Red nyl-6-amino- 8-benzoylamino benzthiazole nuphthalene 3,5-disulfonic acid 4th 2-methylsulfo- 1-hydroxy Red nyl-6-amino- 8-acetylamino benzthiazole naphthalene- 3,5-disulfonic acid 5 2-methylsulfo- 1-hydroxy bluish tint nyl-6-amino- 8-acetylamino Red benzthiazole naphthalene- 3,6-disulfonic acid 6th 2-methylsulfo- 1-hydroxy Scarlet fever nyl-6-amino- naphthalene- benzthiazole 4,7-disulfonic acid 7th 2-methylsulfo- 1-hydroxy Scarlet fever nyl-6-amino- naphthalene- benzthiazole 4,8-disulfonic acid 8th 7-methyl 1-hydroxy Red 6-amino- 8-acetylamino 2-methylsulfonyl- naphthalene- benzthiazole 3,6-disulfonic acid 9 4-sulfo-6-amino- 1-hydroxy Red 2-methylsulfonyl- 8-acetylamino berizthiazole naphthalene- 3,6-disulfonic acid

60

65

Example 10

The prepared according to Example 1 diazo solution of 6-amino-2-methylsulfonyl-benzothiazole is with a neutral solution of 16.5 parts of 1- (4'-sulfophenyl) pyrazolone-5-carboxylic acid-3 offset. The pH value is adjusted to 4 to 5 by adding sodium acetate decreased, with rapid coupling occurs. The dye is filtered off with suction and dried at 50 °. Man receives a yellow powder. The dye obtained has the following composition:

CH ₃ SO

N = N

-COOH

SO ₃ H

If you print cellulose fabric with a printing paste containing 10 g of the dye per kilogram, 100 g urea, 300 ml water, 500 g alginate thickening (60 g sodium alginate per kilogram thickening), Contains 10 g of soda and which was made up to 1 kg with water, dries, 1 minute at 105 ° steamed, rinsed with hot water and soaped at the boil, you get a strong reddish-yellow print of good wet fastness and light fastness.

If one proceeds according to the procedure given in this example, but using the in The diazo and coupling components given in the table below are also valuable Reactive dyes.

No.

Coupling component color

11 2-methylsulfonyl-6-aminobenzothiazole

12 2-methylsulfonyl-6-aminobenzothiazole

13 2-methylsulfonyl-6-amino-

benzthiazole

14 2-methylsulfonyl-6-amino-

benzthiazole

l- (3'-sulfophenyl) -

3-methyl-

pyrazolone-5

l- (2 ', 5'-dichloro-

4'-sulfo-phenyl) -

3-methyl-

pyrazolone-5

l- (4'-sulfophenyl) -

3-methyl-

PyrazoIon-5

l- (2'-methyl-

4'-sulfophenyl) -

3-methyl-

pyrazolone-5

yellow

Example 15

14 parts of 2-methylsulfonyl-6-amino-7-methylbenzthiazole are mixed with 100 parts by volume of ice-water and 16 parts by volume conc. Hydrochloric acid stirred. 4.1 parts of sodium nitrite, which are dissolved in a little water, are collapsed, giving an almost clear yellow solution of the diazonium salt. After the destruction of the Excess nitrite leaves a neutral solution of 18.5 parts of l-hydroxy-7-amino-naphthalene-3,6-di-

Drip sulfonic acid into 100 parts of water; after several hours of stirring, the coupling is complete. After suctioning off and drying at 50 °, a red powder is obtained. The dye corresponds to the following Formula:

were shown, but using different starting components.

No. diazo component

NH ₂ SO ₃ H

CH, SO

IO

CH ₃

SO, H

16

17th

It turns cellulose red.

The table below lists dyes which are analogous to the information in this example Coupling component

PH value
of

Coupling medium

hue

2-methyl

sulfonyl

4-sulfo-

6-amino-

benzthiazole

2-methyl

sulfonyl

6-amino-

benzthiazole

1-hydroxy-7-aminonaphthalene
3-sulfonic acid

2-aminonaphthalene
5,7-disulfonic acid

mineral red
angry

acetic acid

orange

example

To the diazo solution from 6-amino-2-methylsulfonylbenzthiazole prepared according to the instructions in Example 1 becomes a neutral solution of 18.5 parts of 1 - hydroxy - 8 - amino - naphthalene - 3,5 - disulfonic acid dripped in 100 parts by volume of water. After 2 to 3 hours of stirring, the coupling is complete. the Monoazo dye is filtered off with suction, suspended in 100 parts by volume of water, neutralized with soda and after A diazo solution prepared from 10.1 parts of p-sulfanilic acid is added to 10 parts of soda. To brief stirring at 10 °, the coupling is complete. The dye is made by adding potassium chloride deposited. It is a black powder that dissolves in water with a blue color. He corresponds in the form of the free sulfonic acid of the following formula:

NH

OH

HO, S- / V-N = N

HO ₃ S

SO, H

Cotton or regenerated cellulose fabrics can be dyed with the dye as follows will:

50 g of cotton rope are dyed in a dye liquor containing 1.5 g of the above dye, by increasing the temperature from 20 to about 80 ° within 30 minutes, a total of 50 g Add table salt in several portions, then add 20 g trisodium phosphate and 60 minutes treated at this temperature. After rinsing, boiling soaps, and drying, you get one clear, navy blue dyeing of good wet, rub and light fastness.

You can also proceed in such a way that you cotton fabric with a solution of 20 to 25 °, the per liter Liquor 20 g of the above dye and 0.5 g of a nonionic wetting agent (e.g. a polyoxyethylene Oleyl alcohol) as well as 150 g urea and 15 g sodium bicarbonate, impregnated and the fabric then squeezed between two rubber rollers to a moisture content of about 100%. After intermediate drying at 50 to 60 °, the mixture is heated to 140 ° for 10 minutes and the dyeing obtained in this way rinsed thoroughly with hot water and treated boiling for 20 minutes with a solution that pro Liter contains 5 g of Marseille soap and 2 g of soda. After rinsing and drying, you get a strong one navy blue dyeing of good wet, rub and light fastness;

Similar results are obtained if one proceeds as in the application process mentioned first (dyeing from a long liquor), but with the addition of salt and the one-hour aftertreatment with trisodium phosphate not at 80 °, but at room temperature (20 to 30 °). The same applies to the last-mentioned procedure (block dyeing), according to which, as there, with 15 g of sodium bicarbonate or when using 10 g of soda instead of 15 g Sodium bicarbonate, and storing it squeezed to 100% moisture for 5-20 hours Cellulose fabric at room temperature instead of intermediate drying and instead of heating at 140 ° likewise receives blue dyeings with the fastness properties listed above.

The table below lists dyes made from the components specified there using the procedure described in Example 18 analogously.

609623/20

Diazo component for acidic
Coupling closed in o-position
-NH ₂

Middle component

Diazo component for
alkaline coupling in
o-position to -OH

Hue of
Coloring on
Cellulose

19th 2-methylsulfonyl- 1 -hydroxy-8-amino- l-aminobenzene-2-suIfon- navy blue 6-aminobenzothiazole naphthalene-3,5-disulfone- acid acid 20th the same the same Aminobenzene navy blue 21 the same the same 1-aminobenzene-2,5-di- navy blue sulphonic acid 22nd the same the same 1-aminobenzene-2,4-di- navy blue sulfonic acid 23 the same the same l-aminobenzene-3-sulfone navy blue acid 24 the same 1 -hydroxy-8-amino- Aminobenzene greenish naphthalene-3,6-disulfone- dark blue acid 25th the same the same 1-aminobenzene-4-sulfone- greenish acid dark blue 26th the same the same 1-aminobenzene-2-sulfone- greenish acid dark blue 27 the same the same 1-aminobenzene-2,4-di- greenish sulfonic acid dark blue 28 the same the same 1-aminobenzene-2,5-di- greenish sulfonic acid dark blue 29 l-amiftobenzene-4-sulfone the same 2-methylsulfonyl- greenish acid 6-aminobenzothiazole dark blue

example

13.3 parts of 2-methylsulfonyl-6-aminobenzothiazole are diazotized according to the procedure given in Example 1. The diazo solution is added a neutral solution of 10.3 parts of 3-aminoben-ζοΐ-ω-methanesulfonic acid in 50 parts by volume of water. The coupling is completed by adding sodium acetate. The obtained monoazo dye corresponds to the formula

CH ₁ SO.

NH,

CH, SO ₁ H

24.7 parts of this monoazo dye are dissolved neutrally in 200 parts by volume of water and mixed with 4.1 parts Sodium nitrite added. This solution is stirred into a mixture of 16 parts by volume of conc. Hydrochloric acid and 100 volumes divide ice-water. When the diazotization is complete, this becomes a solution of at 10 to 15 ° 17.6 parts of 1 - hydroxynaphthalene - 3,6 - disulfonic acid and 10 parts of soda are added dropwise to 200 parts by volume of water. When the coupling is complete, it is separated out by adding sodium chloride.

The dye paste obtained is dissolved in 1000 parts by volume of water at 50 ° and 80 parts by volume 20% sodium acetate solution and 80 parts by volume of 18% copper sulfate solution are added. Within a Hour 160 parts by volume of 3% hydrogen peroxide are added dropwise until the oxidizing coppering is finished. The copper complex dye is salted out with sodium chloride and isolated. You get a blue-black powder. The dye corresponds to the following formula:

O Cu O

CH ₁ SO- "

I ₃ ClKJ ₂

CH ₂ SO ₃ H SO ₃ H

SO ₃ H

It dyes cotton in strong blue tones.

Example 31

26.2 parts of the dye of the formula

HO

SO, H

SO ₃ H

CH ₁ SO

SO ₃ H

He dyes cotton brown.

Example 32

13.3 parts of 2-methylsulfonyl-6-aminobenzothiazole are diazotized according to the procedure given in Example 1. The diazotization is added dropwise to one Solution of 20.9 parts of 1-hydroxy-8-acetaminonaphthalene-3,6-disulfonic acid and 10 parts of soda in 100 parts by volume of ice-water. When the coupling is complete, the dye is salted out with sodium chloride and sucked off the precipitated dye.

The dye paste obtained is dissolved with 1000 parts by volume of hot water and 80 parts by volume of 20% strength Sodium acetate solution and 80 parts by volume of 18%

Copper (II) sulfate solution added. At a pH from 5 to 6 and a temperature of 50 to 60 ° are about 160 parts by volume within one hour 3% hydrogen peroxide was added dropwise until the oxidizing coppering is complete. The copper complex dye is salted out with sodium chloride and isolated. After drying at 50 °, a dark powder that dissolves in water with a purple color and cotton according to one of the specified Procedure stains purple. In the form of the free sulfonic acid, the dye probably corresponds to the following formula

NHCOCH,

are dissolved neutrally in 200 parts by volume of water and a diazo solution of 13.3 parts of 2-methylsulfonyl-6-aminobenzothiazole added. The coupling is completed by adding sodium acetate. Adding sodium chloride makes the dye deposited. After suctioning off and drying at 50 °, a dark brown powder is obtained, which is in Water with brown color dissolves. The dye obtained corresponds to the following formula

CH.SO.

O-Cu-O

N = N

HO ₃ S

Example 33

SO ₃ H

33.6 parts of 2 - phenylsulfonyl - 6 - aminobenzothiazole are concentrated in 200 parts with stirring. sulfuric acid entered at 0 to 10 °. When solution has occurred, 38 parts of 43.3% nitrosylsulfuric acid become added dropwise at 0 to 10 °. After stirring for one hour in an ice bath, 400 parts of ice are added and add 40 parts of calcined sodium sulfate to the initially clear solution. The diazo compound separates after brief stirring as a thick crystal slurry, which is filtered off with suction and treated with a little saturated sodium chloride solution is washed.

The diazo compound obtained in this way is stirred in 400 parts of ice-water and stirred Adding crystallized sodium acetate to adjust the pH to 1.5. To this suspension is a neutral solution of 37 parts of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid dripped in 200 parts by volume of water.

After several hours of stirring, the acidic coupling has ended. By adding dilute sodium hydroxide solution dropwise is neutralized. After diluting with ice-water and adding 20 parts of soda, a Diazo suspension prepared from 20.2 parts of o-sulfanilic acid added. After the coupling is complete, the dye is obtained at 40 ° to 50 ° by adding sodium chloride deposited. After drying at 50 °, a blue-black powder is obtained, which becomes with blue color dissolves in water. In the form of the free sulfonic acid, the dye corresponds to the formula

NH,

SO ₃ H

-N = N

SO, H

The dyestuff dyes cotton according to one of the components indicated, those with equally good results Procedure in navy blue to black results in this example instead of the 2-phenylsulfo tones of good wet, rub and light fastness. nyl-6-aminobenzothiazoles can be used

Some diazones are shown in the table below.

2- (4'-methylphenylsulfonyl) -6-9.mino-

benzthiazole,

2- (4'-chlorophenylsulfonyl) -6-aminobenzothiazole,
2- (3'-carboxyphenylsulfonyl) -6-amino-

benzthiazole.

Example 34

18.7 parts of 2-ethylsulfonyl-6-amino-benzthiazole-ι ο 5-sulfonic acid are diazotized indirectly. The diazo compound is sucked off. The moist paste is in a neutral solution of 14.7 parts of 1- (4'-sulfophenyl) -3-methyl-pyrazolon-5 entered in 500 parts by volume of ice-water. A pH value of 4 to 5 is maintained by adding sodium acetate. the Dye is deposited with 20% sodium chloride, filtered off with suction and dried at 50 °, it probably corresponds the formula

C ₂ H ₅ SO ₂

CH,

SO ₃ H

The dye dissolves in water with a yellow color. On cotton one gets after one of the given Process a yellow dyeing of good wet and light fastness.

The diazo component used in this example is obtained using the following process:

140 parts of 2 - ethylsulfonyl - 6 - aminobenzothiazole are introduced into 440 parts of sulfuric acid monohydrate. The temperature rises from about 20 to 70 °. At 70 to 80 ° it will take about an hour 670 parts of 20% strength oleum were added dropwise, then heated to 120 ° and kept at this temperature for 1 hour. The mixture is then cooled to room temperature, ice is poured onto 1,300 parts, filtered off with suction and washed with saturated saline solution until a neutral reaction.

If one proceeds according to the procedure given in this example, but using the in Diazo and coupling specified in the following table

C ₂ H ₅ SO

35

treatment components, valuable reactive dyes are also obtained.

Diazo component Coupling component hue 2-ethylsulfonyl- l- (3'-sulfophenyl) - yellow 6-amino-benz- 3-methyl-pyrazolone-5 thiazole-5-sulfone acid 2-ethylsulfonyl- l- (2'-methyl-4'-sulfo- yellow 6-amino-benz- phenyl) -3-methyl- thiazole-5-sulfone pyrazolone-5 acid 2-ethylsulfonyl- l- (4'-sulfophenyl) - Red 6-amino-benz- 3-carboxy pithy thiazole-5-sulfone pyrazolone-5 yellow acid Example 35

18.7 parts of 2-ethylsulfonyl-6-amino-benzothiazole-5-sulfonic acid are diazotized indirectly. The sparingly soluble diazo compound is filtered off with suction. The suspension the diazo compound is dissolved in 500 parts of water with a neutral solution of 12.9 parts 1 - aminonaphthalene - 6 - sulfonic acid added. After several hours of stirring in the acetic acid medium is the clutch ends. The monoazo dye obtained corresponds to the following in the form of the free sulfonic acid Formula:

SO ₃ H

NH,

It is indirectly further diazotized and alkaline bicarbonate to 17.6 parts of 1-hydroxynaphthalene-4,8-disulfonic acid coupled. The disazo dye is deposited by adding table salt. The damp Paste is mixed with 500 parts by volume of water. After adding 80 parts by volume of 20% sodium acetate solution and 80 parts by volume of 18% copper (II) sulfate solution become 150 parts by volume at room temperature 3% hydrogen peroxide solution was added dropwise. The dye is deposited with potassium chloride. He dissolves in water with a dark green color and dyes cotton using one of the specified methods in dark green tones with good lightfastness. It probably corresponds in the form of the free sulfonic acid following formula:

SO ₃ H O-
/ -Cu- SO ₃ H ,H N = N- - / Λ-Ν = = Ν- Ί ρ
SO ₃ H -O
I. ■ Λ V
SO ₃

Example 36

share water. The diazo connection goes to

14 parts of 2 - ethylsulfonyl - 6 - amino - benzothiazole 65 zem stirring with yellow color in solution. Excess in 200 parts by volume of ice-water and 16 parts by volume of nitrite, one removes by adding amidosul parts ko'nz. Hydrochloric acid stirred; here one overthrows a fonsäure. By adding conc. Sodium acetate solution 4.1 parts of sodium nitrite in 10 volume solution are adjusted to pH 1.5. A new

neutral solution of 18.5 parts of 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid in 100 parts by volume of water is added dropwise over the course of an hour. After several hours of stirring, the acidic coupling has ended. It is then neutralized with soda and, after adding 10 parts of soda, with one of 10.1 parts O-sulfanilic acid prepared diazo solution was added. After the coupling is complete, by adding Potassium chloride deposited the dye. When dried, the dye is a black powder that dissolves in water with a blue color. In the form of the free sulfonic acid, it corresponds to the following formula:

NH,

SO ₃ H

OH

_{= N} _ / Vv _N -

The dye dyes cotton in strong navy blue using one of the dyeing processes described to black shades of good wet and rub fastness. Used instead of o-sulfanil- ■ acid m-sulfanilic acid, p-sulfanilic acid, aniline or 2 - amino - naphthalene - disulphonic acid -1.5, you also get dyes that are too strong navy blue lead to black hues on cotton.

Example 37

14 parts of 2 - ethylsulfonyl - 6 - aminobenzothiazole are given as in the previous example Process diazotized. The diazotization is added dropwise to a solution of 17.6 parts of 1-hydroxynaphthalene-4,8-disulfonic acid and 16 parts of sodium bicarbonate in 200 parts by volume of ice-water. To When the coupling is complete, 80 parts by volume of 20% sodium acetate solution and 80 parts by volume of 18% Copper (II) sulfate solution added. 200 parts by volume of 3% strength hydrogen peroxide solution are then added dropwise at room temperature to. The copper complex dye is deposited with potassium chloride. After drying at 50 °, a dark powder is obtained which dissolves in water with a purple color and strong cotton according to one of the specified methods dyes reddish purple shades of good light and wet fastness. Corresponds in the form of the free sulfonic acid the dye probably following the formula:

C ₂ H ₅ SO ₂

O-Cu-O

N = N

SO ₃ H

55

SO ₃ H

The table below lists dyes made from the components specified there can be obtained with analogous application of the procedure described in this example.

Diazo component Coupling component hue 2-ethylsulfonyl- 2-hydroxy-naphtha- ruby 6-aminobenzothiazole lin-3,6-disulfonic acid 2-ethylsulfonyl- 2-hydroxy-naphtha- ruby 6-aminobenzthiazole lin-5,7-disulfonic acid 2-ethylsulfonyl- 2-hydroxy-naphtha- ruby 6-aminobenzothiazole lin-6,8-disulfonic acid 2-ethylsulfonyl- 1-hydroxy-naphtha-. Red 6-aminobenzothiazole lin-3,6- or -4,6- pithy or -4,7-disulfone- violet acid 2-ethylsulfonyl- 1 -hydroxy-naphtha- violet 6-aminobenzothiazole lin-3,6,8-trisulfonic acid 2-ethylsulfonyl- 1 -hydroxy-6-ureido- ruby 6-aminobenzothiazole naphthalene- 3,5-disulfonic acid 2-EthyIsulfonyl- 1 -hydroxy-8-acet- violet 6-aminobenzothiazole amino (or benzoyl- amino) -naphthalene- 3,6-disulfonic acid 2-ethylsulfonyl- 1 -hydroxy-8-acet- violet 6-aminobenzothiazole amino (or benzoyl- amino) -naphthalene- 3,5-disulfonic acid Diazo component Azo component hue

2-methylsulfonyl-

6-amino-

benzthiazole

2-methylsulfonyl-

6-amino-

benzthiazole 2-methylsulfonyl-

6-amino-

benzthiazole

2-methylsulfonyl-

6-amino-

benzthiazole

1-hydroxy-naphtha violet

lin-3,6- or -3,7-

or -4.6- or -4.7-

or -3,8-disulfone-

acid

2-hydroxy naphtha ruby

lin-5- or -6-

-7-sulfonic acid

1-Hydroxy-8-benzoyl violet amino (or acetamino) naphthalmic-3,6-disulfonic acid 1-Hydroxy-8-benzoyl violet (or acetamino) naphthalene-3,5-disulfonic acid

example

18.7 parts of 2-ethylsulfonyl-6-amino-benzothiazole-5-sulfonic acid are diazotized indirectly. The suspension of the diazo compound is made into a solution 18.7 parts of 1 - (2 ', 5' - dichloro - 4 '- sulfophenyl) - 3 - methyl-pyrazolone-5 entered in 200 parts by volume of ice-water, with the simultaneous addition of

609 623/20

Sodium acetate a pH of 4 to 5 is maintained. The dye is made with 20% sodium chloride deposited, filtered off with suction and dried at 50 °. It probably corresponds to the formula:

C ₂ H ₅ SO;

SO ₃ H

N = N

HO

Example 39

18.7 parts of 2-ethylsulfonyl-6-aminobenzothiazole-5-sulfonic acid are diazotized indirectly. The suspension of the diazo compound is made into a solution 24.6 parts of 1-hydroxy-8-benzoylamino-naphthalene-3,5-disulfonic acid and 16 parts of sodium bicarbonate in 100 parts of ice-water. After finished Coupling, the dye is salted out by adding 10 percent by volume of sodium chloride. After Suction, drying at 50 ° in a vacuum drying cabinet and grinding gives a red powder that dissolves in water with a clear red color.

The dye probably corresponds to the following formula:

SO, H

C ₂ H ₅ SO ₂

OH

SO ₃ H

The dye, which is readily soluble in water with a yellow color, is like a dye for reactive cotton dyes usual impregnation process a strong yellow coloration with excellent light and wet fastness. The table below lists dyes obtained from the coupling components specified there according to the procedure described in this example and using the 2-ethylsulfonyl - 6 - amino - benzothiazole - 5 - sulfonic acid or 2-methylsulfonyl-6-aminobenzothiazole-5-sulfonic acid can be obtained as a diazo component.

N = N

HO ₁ S

NH-CC ₆ H ₅

¹ Il ο

SO, H

Coupling component

hue

1- (2'-chloro-4'-sulfophenyl) -3-methylpyrazolone-5

1- (2'-chloro-5'-sulfophenyl) -3-methylpyrazolone-5

1- (2 ', 5'-disulfophenyl) -3-methylpyrazolone-5

1- (6'-chloro-4'-sulfo-2'-methyl-phenyl) -3-methyl-pyrazolone-5

1- (4'-Sulfo-2'-methyl-phenyl) -pyrazolone-5-carboxylic acid-3

1- (4'-sulfophenyl) -3-methyl-5-aminopyrazole

1- (3'-sulfophenyl -) - 3-methyl-5-aminopyrazole

1- (2 ', 5'-dichloro-4'-sulfophenyl -) - 3-methyl-5-pyrazole

1 - (2'-chloro-4'-sulfophenyl) -3-methy 1-5-aminopyrazole

1- (2'-chloro-5'-sulfophenyl) -3-methyl-5-aminopyrazole

1- (2'-methyl-4'-sulfophenyl) -3-methyl-5-aminopyrazole

yellow yellow yellow yellow

red-tinged yellow green-tinged yellow green-tinged yellow green-tinged Yellow, greenish yellow, greenish yellow, greenish yellow It dyes cotton according to a method used for reactive dyes usual processes in blue-tinged red tones, which are characterized by very good washfastness and lightfastness distinguish. The coloring can be etched in pure white.

_# If, instead of the coupling component used in this example, the compounds listed in the table below are used as coupling components and 2-ethylsulfonyl-6-aminobenzothiazole-5-sulfonic acid or the corresponding methylsulfonyl compound as diazo component, valuable reactive dyes are also obtained.

Hue on
cotton

1 -Benzoylamino-8-hydroxy- bluish-tinted red

naphthalene-3,6-disulfonic acid

l-acetylamino-8-hydroxy-bluish-tinted red

naphthalene-3,6-disulfonic acid
l-acetylamino-8-hydroxy red

naphthalene-4,6-disulfonic acid
2-acetylamino-5-hydroxy- reddish-

naphthalene-7-sulfonic acid orange

2-benzoylamino-5-hydroxy-scarlet

naphthalene-7-sulfonic acid
2-benzoylamino-5-hydroxy-scarlet

naphthalene-1,7-disulfonic acid
2-acetylamino-8-hydroxy-yellowish red

naphthalene-6-sulfonic acid

2-benzoylamino-8-hydroxy red

naphthalene-6-sulfonic acid
2-benzoylamino-S-hydroxy red

naphthalene-3,6-disulfonic acid

2- (3'-sulfophenyl-amino) - brown

S-hydroxy-naphthalene-o-sulfonic acid
2- (4'-sulfophenyl-amino) -. Brown

S-hydroxy-naphthalene-6-sulfonic acid
2- (2 ', 5'-disulfophenyl-amino) - brown

8-hydroxy-naphthalene-6-sulfonic acid

continuation

Hue on
cotton

1 -hydroxy-naphthalene-5-sulfone-

2-hydroxy naphthalene

3,6-disulfonic acid

1 - hydroxy-6-acetylamino-

naphthalene-4,8-disulfonic acid

1-hydroxynaphthalene-4-sulfonic acid

2-hydroxy-6-carboxy-

naphthalene-6-sulfonic acid

1 -acetylamino-5-hydroxy-

naphthalene-7-sulfonic acid

1 -Benzoylamino-5-hydroxy-

naphthalene-7-sulfonic acid

l-benzoylamino-8-hydrpxy-

naphthalene-4-sulfonic acid

1 -acetylamino-8-hydroxy-

naphthalene-4-sulfonic acid

1 -acetylamino-3-hydroxy-

naphthalene-6-sulfonic acid

2-benzoylamino-3-hydroxy

naphthalene-6-sulfonic acid

l-chloro ^ -acetylamino-S-hydroxy-

naphthalene-7-sulfonic acid

1-hydroxy-naphthalene-

3,6-disulfonic acid

1 -hydroxy-naphthalene-

3,7-disulfonic acid

Red
Red
Red

Red
Red

Red

Red

bluish red

bluish red

Red

Red

reddish orange

yellowish red

yellowish red

NH,

HO ₃ S

HO, S

With a printing paste of 80 parts of the dye prepared according to this embodiment, 200 parts Urea, 200 parts of water, 500 parts of a thickener containing 3% sodium alginate, 10 parts l-nitrobenzene-3-sodium sulfonate and 10 parts Soda is printed on a piece of cotton nettle. The dried fabric is steamed for 1 minute at 102 °, then rinsed, soaped at the boil and dried. A black print of excellent quality is obtained Fastness to washing.

If, instead of the 1-amino-benzene-2,5-disulfonic acid used as the diazo component in this example l-amino-4-methylbenzene-2-sulfonic acid, 1 - amino - 4 - chlorobenzene - 2 - sulfonic acid, 1 - amino - 5 - chlorobenzene - 2 - sulfonic acid or the 4 - amino - azobenzene - 3,4 '- disulfonic acid used, Valuable dyes are also obtained in this way, the cotton according to one of the usual for reactive dyes Color process in navy blue to black tones.

Example 41

17.9 parts of 2-methylsulfonyl-6-aminobenzothiazole-5-sulfonic acid are diazotized indirectly. The suspension of the diazo compound is dissolved in a solution of 24.6 parts of 1-hydroxy-8-benzoylamino-naphthalene hue
cotton

1-hydroxy-naphthalene-4,6-disulfonic acid

1-hydroxy-naphthalene-3,8-disulfonic acid

1-hydroxy-naphthalene-4,8-disulfonic acid

1-hydroxy-naphthalene-4,7-disulfonic acid

yellowish red
yellowish red
yellowish red
yellowish red

Example 40

14 parts of 2-ethylsulfonyl-6-amino-benzothiazole are in 200 parts by volume of ice-water and 16 parts by volume conc. Hydrochloric acid stirred; a solution of 4.1 parts of sodium nitrite in 10 parts by volume is poured into it Water. After brief stirring, the diazo compound goes into solution with a yellow color. After removal the excess nitrite with sulfamic acid is obtained by adding conc. Sodium acetate solution the pH is set to 1.5. A neutral solution of 18.5 parts of 1 - hydroxy - 8 - amino - naphthalene - 3,6 - disulfonic acid in 100 parts by volume of water is added dropwise over the course of an hour. After stirring for several hours the acidic coupling is over. Then it is neutralized with dilute sodium hydroxide solution and after Addition of 10 parts of soda with a diazo solution prepared from 14.7 parts of aniline-2,5-disulfonic acid. When the coupling is complete, the dye is isolated by spray drying. The dye corresponds in the form of the free sulfonic acid of the following formula:

N = N

SO ₁ H

3,5-disulfonic acid and 16 parts of bicarbonate in 100 parts Entered ice water. After the coupling is complete, sodium chloride is added by adding 10 percent by volume the dye is salted out. After vacuuming, drying at 50 ° in a circulating air drying cabinet and grinding gives a red powder which dissolves in water with a red color. The dye corresponds probably the following formula:

CH, S O

55

60

SO ₃ H

N = N

HO ₃ S

OH

NH-CC ₆ H ₅ O

SO, H

It dyes cotton in reddish blue shades of very good washfastness and lightfastness.
If the procedure given in this example is followed, but using 21.5 parts of 2-phenylsulfonyl-6-aminobenzothiazole-5-sulfonic acid, a valuable reactive dye is likewise obtained.

Claims (1)

Patent claims:
1. Water-soluble azo dyes of the formula ^Rs °; - < _S X ^ ^{N == N} + -A-S In wherein A is a radical of an aminobenzene, aminonaphthalenes, pyrazolones, hydroxybenzenes, hydroxynaphthalene, aminopyrazole and acetoacetic acid amide, the substituent S being sulfonic acid, carboxylic acid, sulfamide, sulfonic, alkylamino, nitro, cyano, halogen, hydroxy, Alkoxy, mono-, di- or trihalogenopyrimidinamino-, monohalogeno- or dihalotriazinylamino groups, R _{1 is} hydrogen or the sulfo- wherein C is hydrogen or chlorine, bromine or methyl, £ the number 1 or 2, R is an alkyl having 1 to 5 carbon atoms, optionally phenyl substituted by chlorine or methyl, benzyl or the 2-benzthiazolyl radical, R _{1 is} hydrogen or the sulfo group, X is Radical O = or HN = and η denotes the number 1 or 2.
4. Water-soluble azo dyes of the formula NH ₉ RSO 45 D (SO ₃ H), where D is hydrogen, the hydroxyl or the acetylamino or the benzoylamino group, t is the number 1 or 2, R is an alkyl having 1 to 5 carbon atoms, optionally phenyl substituted by chlorine or methyl, benzyl or the 2-benzothiazolyl radical, R _{1 is} hydrogen or sulfo group. 5. Water-soluble azo dyes of the formula OH 60 NH -N = N N = N-E (SO ₃ H), 65 where E is the radical of a benzene or naphthalene nucleus, which is optionally substituted by chlorine, the Hy group, R is an alkyl radical having 1 to 5 carbon atoms, phenyl, benzyl or 2-benzothiazolyl radical which is optionally substituted by chlorine or methyl, η is the number 1 or 2. 2. Water-soluble azo dyes of the formula RSO. < ^so » ^h >. where B is hydrogen or the acetyl or benzoylamino, alkoxy substituent, u is an integer from 1 to 3, R is an alkyl radical having 1 to 5 carbon atoms, optionally phenyl, benzyl or 2-benzthiazolyl substituted by chlorine or methyl and R ₁ denotes hydrogen or the sulfo group. 3. Water-soluble azo dyes of the formula CH ₃ or - COOH R —SO, (SO ₃ H) ₁ may be substituted hydroxy or nitro or sulfo groups or the remainder of the formula t is the number 1 or 2, R is an alkyl having 1 to 5 carbon atoms, phenyl, benzyl or the 2-benzothiazolyl radical which is optionally substituted by chlorine or methyl, and R _{1 is} hydrogen or the sulfo group.
6. Water-soluble azo dyes of the formula RSO. OH wherein F is a phenyl radical substituted by one or more sulfonic acid groups, in which the azo and - O groups are in the o-position to one another, R is an alkyl having 1 to 5 carbon atoms, optionally phenyl substituted by chlorine or methyl, benzyl or the 2 -Benzthiazolyl radical and R _{1 is} hydrogen or the sulfo group. 7. Water-soluble azo dyes of the formula R ₁ Ki where G is the acetyl or benzoyl group, K ₁ and K _{2 are} hydrogen or methyl, methoxy, acetyl or benzoylamino groups or an ω-methanesulfonic acid group, R is an alkyl having 1 to 5 carbon atoms, optionally phenyl, benzyl or substituted by chlorine or methyl the 2-benzothiazolyl radical and R _{1 is} hydrogen or sulfo.
8. Water-soluble azo dyes of the formula O-Cu-O RSO ₂ K ₁ where B is hydrogen, the acetyl or benzoylamino or alkoxy group, K _{1 is} hydrogen or a methyl, methoxy, acetyl or benzoylamino group or an ω-methanesulfonic acid group, u is an integer from 1 to 3, R is an alkyl radical having 1 to 5 carbon atoms , phenyl optionally substituted by chlorine or methyl, benzyl or the 2-benzthiazolyl radical and R ₁ denotes hydrogen or sulfo.
9. Water-soluble azo dyes of the formula OH N = N RSO ₂ (SO ₃ H) ₁ , 5 carbon atoms, phenyl, benzyl or the 2-benzothiazolyl radical, optionally substituted by chlorine or methyl, and R ₁ denotes hydrogen or the sulfo group. 10. Water-soluble azo dyes of the formula 35 N = N-E 40 (SO ₃ H), where E is the radical of one of the diazo components specified in more detail in the description, preferably one of the benzene or naphthalene series, t is the number 1 or 2, R is an alkyl radical with 1 to (SO ₃ H), where t is the number 1 or 2, R is an alkyl radical having 1 to 5 carbon atoms, phenyl, benzyl or the 2-benzothiazolyl radical which is optionally substituted by chlorine or methyl, and R _{1 is} hydrogen or the sulfo group. 11. Water-soluble azo dyes of the formula O — Cu N = N (SO ₃ H) ₁ , where B is hydrogen, an acetylamino, benzoylamino, alkoxy or arylamino group, u is an integer from 1 to 3, R is an alkyl radical with 1 to 5 carbon atoms, optionally phenyl, benzyl or 2-benzthiazolyl which is substituted by chlorine or methyl and R ₁ denotes hydrogen or the sulfo group. 12. Use of the dyes of claims 1 to U for dyeing and printing cellulosic materials.